CA2642603A1 - Process for preparing alkoxypolyoxyalkylene (meth)acrylates - Google Patents
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Abstract
A process for preparing an alkoxypolyoxyalkylene (meth)acrylate, in which a) a metal alkoxide MetOR10 is initially charged, b) an alkylene oxide of the formula (IV) is added and reacted with the metal alkoxide, and c) (meth)acrylic anhydride is added directly and reacted with the reaction product from step b). Appropriately, a stabilizer mixture is added in step c) which comprises, for example, the following components: at least one compound of the formula (I); at least one compound of the formula (IIa or IIb) or of the formula (IV); at least one compound of the formula (V).
Description
Process for preparing alkoxypolyoxyalkylene (meth)acrylates Field of the invention The present invention relates to a process for preparing alkoxypolyoxyalkylene (meth) acrylates, and to a stabilizer mixture which is particularly appropriate for this process.
State of the art DE 10 2004 042799 (BASF) describes the preparation of polyethylene glycol (meth)acrylates with catalysis by catalysts which, at 90 degrees Celsius, have a solubility in polyethylene glycol of not more than 10 g/litre. The catalysts used are hydroxides, oxides, carbonates or hydrogen carbonates of mono- or divalent alkali metals or alkaline earth metals.
Alkoxypolyoxyalkylene (meth)acrylates are already known and are proposed, for example, in the Patent Application EP 0 965 605 A2 (NOF Corporation) for the preparation of dispersants. The alkoxypolyoxyalkylene (meth)acrylates are prepared by adding a catalyst, for example p-toluenesulphonic acid monohydrate, to a polyoxyalkylene monoalkyl ether and subsequently performing an esterification with acrylic acid or methacrylic acid, by adding a catalyst, for example sodium methoxide, to a polyoxyalkylene monoalkyl ether and subsequently transesterifying with an alkyl acrylate, for example methyl acrylate, or with an alkyl methacrylate, for example methyl methacrylate, by reacting a polyoxyalkylene monoalkyl ether with acryloyl chloride or methacryloyl chloride, or by reacting a polyoxyalkylene monoalkyl ether with acrylic anhydride or methacrylic anhydride.
In EP 0 965 605 A2, Examples 7-11 and Comparative Examples 3 and 4 illustrate the preparation routes. In Examples 7, 9-11 and Comparative Examples 3 and 4, an alkoxide, for example sodium methoxide, is initially charged, reacted with an alkylene oxide, for example ethylene oxide, propylene oxide or an alkylene oxide mixture of propylene oxide and 1,2-butylene oxide, neutralized with hydrochloric acid and then esterified with acrylic acid or methacrylic acid in toluene with catalysis by p-toluenesulphonic acid. The stabilizer used is hydroquinone.
In Example 8 of the abovementioned application, sodium methoxide is reacted with ethylene oxide in methanol and neutralized with hydrochloric acid, and the product is isolated and dried, admixed again with sodium methoxide in methanol and transesterified with methyl methacrylate.
The stabilizer added is t-butylhydroxytoluene.
Even though the processes described above are suitable in principle for preparing alkoxypolyoxyalkylene (meth)acrylates, more efficient and less expensive routes to the preparation are nevertheless desirable.
Problem and solution It is therefore an object of the present invention to specify an improved process for preparing alkoxypolyoxyalkylene (meth)acrylates. This process should enable the preparation of the alkoxypolyoxyalkylene (meth)acrylates in a particularly simple manner, on the industrial scale and inexpensively, in high quality and with acceptable reaction rates.
State of the art DE 10 2004 042799 (BASF) describes the preparation of polyethylene glycol (meth)acrylates with catalysis by catalysts which, at 90 degrees Celsius, have a solubility in polyethylene glycol of not more than 10 g/litre. The catalysts used are hydroxides, oxides, carbonates or hydrogen carbonates of mono- or divalent alkali metals or alkaline earth metals.
Alkoxypolyoxyalkylene (meth)acrylates are already known and are proposed, for example, in the Patent Application EP 0 965 605 A2 (NOF Corporation) for the preparation of dispersants. The alkoxypolyoxyalkylene (meth)acrylates are prepared by adding a catalyst, for example p-toluenesulphonic acid monohydrate, to a polyoxyalkylene monoalkyl ether and subsequently performing an esterification with acrylic acid or methacrylic acid, by adding a catalyst, for example sodium methoxide, to a polyoxyalkylene monoalkyl ether and subsequently transesterifying with an alkyl acrylate, for example methyl acrylate, or with an alkyl methacrylate, for example methyl methacrylate, by reacting a polyoxyalkylene monoalkyl ether with acryloyl chloride or methacryloyl chloride, or by reacting a polyoxyalkylene monoalkyl ether with acrylic anhydride or methacrylic anhydride.
In EP 0 965 605 A2, Examples 7-11 and Comparative Examples 3 and 4 illustrate the preparation routes. In Examples 7, 9-11 and Comparative Examples 3 and 4, an alkoxide, for example sodium methoxide, is initially charged, reacted with an alkylene oxide, for example ethylene oxide, propylene oxide or an alkylene oxide mixture of propylene oxide and 1,2-butylene oxide, neutralized with hydrochloric acid and then esterified with acrylic acid or methacrylic acid in toluene with catalysis by p-toluenesulphonic acid. The stabilizer used is hydroquinone.
In Example 8 of the abovementioned application, sodium methoxide is reacted with ethylene oxide in methanol and neutralized with hydrochloric acid, and the product is isolated and dried, admixed again with sodium methoxide in methanol and transesterified with methyl methacrylate.
The stabilizer added is t-butylhydroxytoluene.
Even though the processes described above are suitable in principle for preparing alkoxypolyoxyalkylene (meth)acrylates, more efficient and less expensive routes to the preparation are nevertheless desirable.
Problem and solution It is therefore an object of the present invention to specify an improved process for preparing alkoxypolyoxyalkylene (meth)acrylates. This process should enable the preparation of the alkoxypolyoxyalkylene (meth)acrylates in a particularly simple manner, on the industrial scale and inexpensively, in high quality and with acceptable reaction rates.
In the text which follows, the term (meth)acrylates means both acrylates and methacrylates, and also mixtures of the two compounds.
It has been found, surprisingly, that this object can be achieved by a process in which a reactor a) is initially charged with at least one metal alkoxide MetORlo, b) at least one alcohol R12OH is added, c) at least one alkylene oxide of the formula (VI) is added and reacted with the metal alkoxide/alcohol mixture R O R
(VI) ~iR Rtt d) then (meth)acrylic anhydride is added directly and reacted with the reaction product from step c) and then optionally with water.
The inventive procedure allows a"one-pot synthesis", i.e. an isolation and purification of intermediates is no longer required.
The present invention therefore relates to a process for preparing poly(oxyalkylene) monoacrylic esters and monomethacrylic esters by reacting acrylic anhydride or methacrylic anhydride (hereinafter (meth) acrylic anhydride A) with a reaction product formed from d) at least one metal alkoxide MetORlo e) at least one alcohol R12OH
It has been found, surprisingly, that this object can be achieved by a process in which a reactor a) is initially charged with at least one metal alkoxide MetORlo, b) at least one alcohol R12OH is added, c) at least one alkylene oxide of the formula (VI) is added and reacted with the metal alkoxide/alcohol mixture R O R
(VI) ~iR Rtt d) then (meth)acrylic anhydride is added directly and reacted with the reaction product from step c) and then optionally with water.
The inventive procedure allows a"one-pot synthesis", i.e. an isolation and purification of intermediates is no longer required.
The present invention therefore relates to a process for preparing poly(oxyalkylene) monoacrylic esters and monomethacrylic esters by reacting acrylic anhydride or methacrylic anhydride (hereinafter (meth) acrylic anhydride A) with a reaction product formed from d) at least one metal alkoxide MetORlo e) at least one alcohol R12OH
f) at least one alkylene oxide of the formula (VI) 11 R 0 Rt~
%~ (VI), iiR Rti wherein the end product, after the reaction has ended, is optionally admixed with water, and the methacrylic anhydride is used in a molar ratio, based on the reaction product of the metal alkoxide MetOR10, the alcohol R120H
and the alkylene oxide of the formula (VI), which is between 1:1 and 3:1.
The process according to the invention is associated with a series of advantages. Firstly, separate provision of monofunctional polyoxyalkylene raw materials bearing OH
groups is no longer necessary, and, secondly, shorter reaction times are achieved overall than in the method in two separate reactions, which is the current state of the art.
In addition, improved means of stabilizing the reaction mixture and the resulting product were to be indicated.
It has been found that, surprisingly, suitable selection of the stabilizers or of the stabilizer mixture, especially those which are water-soluble and unreactive toward methacrylic anhydride, considerably prolongs the stability time of the monomer.
This object and further objects which have not been described specifically but which can be discerned from the above-described connections are achieved by a process for preparing alkoxypolyoxyalkylene (meth)acrylates having all features of the present independent process claims. The dependent process claims describe particularly advantageous procedures for preparing alkoxypolyoxyalkylene (meth)acrylates. Further product claims protect a stabilizer mixture whose use in the present process is very particularly appropriate.
In the process according to the invention, at least one metal alkoxide MetORl is first initially charged. The Met radical is lithium, sodium, potassium, rubidium or caesium, preferably lithium, sodium or potassium, in particular sodium or potassium, more preferably sodium.
It is also possible for a metal hydroxide to be initially charged, in which case dewatering of the reaction solution before the addition of the alkylene oxide is required.
R10 is a linear or branched alkyl radical, preferably having 1 to 18 carbon atoms, especially a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or an octadecyl radical. R10 may also be hydrogen.
Particular preference is given to a radical which has 1 to 4 carbon atoms.
R12 is a linear or branched, optionally alkoxylated alkyl radical, preferably having 1 to 18 carbon atoms, in particular a methyl, 2-methoxyethyl, 2-(2-methoxyethoxy)ethyl, 2-(2-(2-methoxyethoxy)ethoxy)-ethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or an octadecyl radical, where the molar mass of R12 is less than the molar mass of the inventive alkoxypolyoxyalkylenes.
Particular preference is given to a radical which has 1 to 4 carbon atoms.
In the process according to the invention, at least one alkylene oxide of the formula (VI) is then added and it is reacted with the metal alkoxide.
11R 4 Rll ~ (VI) 11R Rit The R11 radicals are each independently hydrogen or a linear or branched alkyl radical, preferably having 1 to 8 carbon atoms, especially a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl or an n-octyl radical. A radical which has 1 to 4 carbon atoms is particularly preferred.
In this context, ethylene oxide, propylene oxide and 1,2-butylene oxide, and also mixtures of these compounds, have been found to be very particularly useful.
The reaction of the metal alkoxide with the alkylene oxide is preferably performed in a reactive solvent R120H.
A particularly favourable solvent is the alcohol whose alkoxide is reacted with the alkylene oxide.
The length of the polyalkylene block can be adjusted via the molar ratio of inetal alkoxide and alcohol R120H on the one hand to alkylene oxide on the other. It is preferably in the range of 1:1-10 000, appropriately in the range of 1:1-1000, especially in the range of 1:1-100.
The reaction is appropriately performed at a temperature in the range of 600C to 1500C, preferably in the range of 800C to 1200C, especially in the range of 900C to 1100C.
The reaction time is preferably in the range of 1 to 20 hours, preferably in the range of 2 to 10 hours, especially in the range of 4 to 8 hours.
After the reaction, any excess alkylene oxide can be removed, for example by applying a reduced pressure.
The reaction product from the reaction of the metal alkoxide and alcohol with the alkylene oxide is reacted directly with (meth)acrylic anhydride, i.e. without isolating and/or purifying the intermediate. The expression (meth)acrylic anhydride encompasses both methacrylic anhydride and acrylic anhydride, and also mixtures of the two compounds.
In the context of the present invention, the (meth)acrylic anhydride, based on the sum of the metal alkoxide and the alcohol, is preferably used in excess, preferably in a molar ratio of (meth)acrylic anhydride to metal alkoxide of greater than 1, especially in the range of 1-3:1.
The reaction is appropriately performed at a temperature in the range of 600C to 1500C, preferably in the range of 700C to 1100C, especially in the range of 800C to 1000C.
The reaction time is preferably in the range of 1 to 20 hours, preferentially in the range of 2 to 10 hours, especially in the range of 4 to 8 hours.
The stabilizers and the stabilizer mixtures In addition, the reaction is appropriately performed in the presence of at least one stabilizer or one stabilizer mixture. In the context of the present invention, stabilizers (antioxidants) denote preferably organic compounds which are intended to prevent undesired polymerization of the methacrylic anhydride and/or of the alkoxypolyoxyalkylene (meth)acrylate. The action of the stabilizers usually consists in acting as free-radical scavengers for the free radicals which occur in the polymerization. For further details, reference is made to the common technical literature, especially to the Rompp-Lexikon Chemie; Editors: J. Falbe, M. Regitz; Stuttgart, New York; 10th edition (1996) ; under "Antioxidants", and the literature references cited at this point.
Stabilizers particularly suitable for the purposes of the present invention include tocopherol, tert-butylmethoxyphenol (BHA), butylhydroxytoluene (BHT), octyl gallate, dodecyl gallate, ascorbic acid, optionally substituted phenols, optionally substituted hydroquinones, for example hydroquinone monomethyl ether (HQME), optionally substituted quinones, optionally substituted pyrocatechols, optionally substituted aromatic amines, optionally substituted metal complexes of an aromatic amine, optionally substituted triazines, organic sulphides, organic polysulphides, organic dithiocarbamates, organic phosphites and organic phosphonates.
Substituted phenols Optionally substituted phenols are used with very particular preference in accordance with the invention.
These preferably satisfy the formula (I) OH
~R Ri ~ {I) ~ R Ri where the R1 radicals are each independently hydrogen, a linear or branched alkyl radical, preferably having 1 to 8 carbon atoms, especially a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl or an n-octyl radical, which favourably has 1 to 4 carbon atoms, an optionally substituted cycloalkyl radical, preferably having 4 to 8 carbon atoms, especially a cyclohexyl radical, an optionally substituted aryl radical, preferably having 6 to 18 carbon atoms, or a halogen, preferably fluorine, chlorine or bromine, and where Rz is a linear or branched alkyl radical, preferably having 1 to 8 carbon atoms, especially a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl or is an n-octyl radical, which more preferably has 1 to 4 carbon atoms, is an optionally substituted cycloalkyl radical, preferably having 4 to 8 carbon atoms, especially a cyclohexyl radical, or is an optionally substituted aryl radical, preferably having 6 to 18 carbon atoms.
Compounds (I) which are very particularly favourable in this context have hydrogen as R1. R2 is preferably an alkyl radical having 1 to 4 carbon atoms, especially a methyl radical.
It has also been found that compounds of the formula (II) are particularly useful for the purposes of the present invention OH
0 (II) RS
where the R3, R4 and R5 radicals are each independently hydrogen, a linear or branched alkyl radical, preferably having 1 to 8 carbon atoms, especially a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl or an n-octyl radical, which more preferably has 1 to 4 carbon atoms, an optionally substituted cycloalkyl radical, preferably having 4 to 8 carbon atoms, especially a cyclohexyl radical, an optionally substituted aryl radical, preferably having 6 to 18 carbon atoms, a halogen, preferably fluorine, chlorine or bromine, or a radical of the formula (III) O
~
O ~ R 6 ~zzz>
in which R6 is a linear or branched alkyl radical having 1 to 6 carbon atoms, preferably a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl or n-hexyl radical, especially an ethyl radical.
Compounds (II) which are very particularly favourable in this context have hydrogen as R4. R3 is preferably an alkyl radical having 1 to 4 carbon atoms, especially a methyl radical. R5 is appropriately an alkyl radical having 1 to 4 carbon atoms, especially a tert-butyl radical.
For the purposes of the present invention, compounds of the formula (IIa) have also been found to be suitable.
%~ (VI), iiR Rti wherein the end product, after the reaction has ended, is optionally admixed with water, and the methacrylic anhydride is used in a molar ratio, based on the reaction product of the metal alkoxide MetOR10, the alcohol R120H
and the alkylene oxide of the formula (VI), which is between 1:1 and 3:1.
The process according to the invention is associated with a series of advantages. Firstly, separate provision of monofunctional polyoxyalkylene raw materials bearing OH
groups is no longer necessary, and, secondly, shorter reaction times are achieved overall than in the method in two separate reactions, which is the current state of the art.
In addition, improved means of stabilizing the reaction mixture and the resulting product were to be indicated.
It has been found that, surprisingly, suitable selection of the stabilizers or of the stabilizer mixture, especially those which are water-soluble and unreactive toward methacrylic anhydride, considerably prolongs the stability time of the monomer.
This object and further objects which have not been described specifically but which can be discerned from the above-described connections are achieved by a process for preparing alkoxypolyoxyalkylene (meth)acrylates having all features of the present independent process claims. The dependent process claims describe particularly advantageous procedures for preparing alkoxypolyoxyalkylene (meth)acrylates. Further product claims protect a stabilizer mixture whose use in the present process is very particularly appropriate.
In the process according to the invention, at least one metal alkoxide MetORl is first initially charged. The Met radical is lithium, sodium, potassium, rubidium or caesium, preferably lithium, sodium or potassium, in particular sodium or potassium, more preferably sodium.
It is also possible for a metal hydroxide to be initially charged, in which case dewatering of the reaction solution before the addition of the alkylene oxide is required.
R10 is a linear or branched alkyl radical, preferably having 1 to 18 carbon atoms, especially a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or an octadecyl radical. R10 may also be hydrogen.
Particular preference is given to a radical which has 1 to 4 carbon atoms.
R12 is a linear or branched, optionally alkoxylated alkyl radical, preferably having 1 to 18 carbon atoms, in particular a methyl, 2-methoxyethyl, 2-(2-methoxyethoxy)ethyl, 2-(2-(2-methoxyethoxy)ethoxy)-ethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or an octadecyl radical, where the molar mass of R12 is less than the molar mass of the inventive alkoxypolyoxyalkylenes.
Particular preference is given to a radical which has 1 to 4 carbon atoms.
In the process according to the invention, at least one alkylene oxide of the formula (VI) is then added and it is reacted with the metal alkoxide.
11R 4 Rll ~ (VI) 11R Rit The R11 radicals are each independently hydrogen or a linear or branched alkyl radical, preferably having 1 to 8 carbon atoms, especially a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl or an n-octyl radical. A radical which has 1 to 4 carbon atoms is particularly preferred.
In this context, ethylene oxide, propylene oxide and 1,2-butylene oxide, and also mixtures of these compounds, have been found to be very particularly useful.
The reaction of the metal alkoxide with the alkylene oxide is preferably performed in a reactive solvent R120H.
A particularly favourable solvent is the alcohol whose alkoxide is reacted with the alkylene oxide.
The length of the polyalkylene block can be adjusted via the molar ratio of inetal alkoxide and alcohol R120H on the one hand to alkylene oxide on the other. It is preferably in the range of 1:1-10 000, appropriately in the range of 1:1-1000, especially in the range of 1:1-100.
The reaction is appropriately performed at a temperature in the range of 600C to 1500C, preferably in the range of 800C to 1200C, especially in the range of 900C to 1100C.
The reaction time is preferably in the range of 1 to 20 hours, preferably in the range of 2 to 10 hours, especially in the range of 4 to 8 hours.
After the reaction, any excess alkylene oxide can be removed, for example by applying a reduced pressure.
The reaction product from the reaction of the metal alkoxide and alcohol with the alkylene oxide is reacted directly with (meth)acrylic anhydride, i.e. without isolating and/or purifying the intermediate. The expression (meth)acrylic anhydride encompasses both methacrylic anhydride and acrylic anhydride, and also mixtures of the two compounds.
In the context of the present invention, the (meth)acrylic anhydride, based on the sum of the metal alkoxide and the alcohol, is preferably used in excess, preferably in a molar ratio of (meth)acrylic anhydride to metal alkoxide of greater than 1, especially in the range of 1-3:1.
The reaction is appropriately performed at a temperature in the range of 600C to 1500C, preferably in the range of 700C to 1100C, especially in the range of 800C to 1000C.
The reaction time is preferably in the range of 1 to 20 hours, preferentially in the range of 2 to 10 hours, especially in the range of 4 to 8 hours.
The stabilizers and the stabilizer mixtures In addition, the reaction is appropriately performed in the presence of at least one stabilizer or one stabilizer mixture. In the context of the present invention, stabilizers (antioxidants) denote preferably organic compounds which are intended to prevent undesired polymerization of the methacrylic anhydride and/or of the alkoxypolyoxyalkylene (meth)acrylate. The action of the stabilizers usually consists in acting as free-radical scavengers for the free radicals which occur in the polymerization. For further details, reference is made to the common technical literature, especially to the Rompp-Lexikon Chemie; Editors: J. Falbe, M. Regitz; Stuttgart, New York; 10th edition (1996) ; under "Antioxidants", and the literature references cited at this point.
Stabilizers particularly suitable for the purposes of the present invention include tocopherol, tert-butylmethoxyphenol (BHA), butylhydroxytoluene (BHT), octyl gallate, dodecyl gallate, ascorbic acid, optionally substituted phenols, optionally substituted hydroquinones, for example hydroquinone monomethyl ether (HQME), optionally substituted quinones, optionally substituted pyrocatechols, optionally substituted aromatic amines, optionally substituted metal complexes of an aromatic amine, optionally substituted triazines, organic sulphides, organic polysulphides, organic dithiocarbamates, organic phosphites and organic phosphonates.
Substituted phenols Optionally substituted phenols are used with very particular preference in accordance with the invention.
These preferably satisfy the formula (I) OH
~R Ri ~ {I) ~ R Ri where the R1 radicals are each independently hydrogen, a linear or branched alkyl radical, preferably having 1 to 8 carbon atoms, especially a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl or an n-octyl radical, which favourably has 1 to 4 carbon atoms, an optionally substituted cycloalkyl radical, preferably having 4 to 8 carbon atoms, especially a cyclohexyl radical, an optionally substituted aryl radical, preferably having 6 to 18 carbon atoms, or a halogen, preferably fluorine, chlorine or bromine, and where Rz is a linear or branched alkyl radical, preferably having 1 to 8 carbon atoms, especially a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl or is an n-octyl radical, which more preferably has 1 to 4 carbon atoms, is an optionally substituted cycloalkyl radical, preferably having 4 to 8 carbon atoms, especially a cyclohexyl radical, or is an optionally substituted aryl radical, preferably having 6 to 18 carbon atoms.
Compounds (I) which are very particularly favourable in this context have hydrogen as R1. R2 is preferably an alkyl radical having 1 to 4 carbon atoms, especially a methyl radical.
It has also been found that compounds of the formula (II) are particularly useful for the purposes of the present invention OH
0 (II) RS
where the R3, R4 and R5 radicals are each independently hydrogen, a linear or branched alkyl radical, preferably having 1 to 8 carbon atoms, especially a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl or an n-octyl radical, which more preferably has 1 to 4 carbon atoms, an optionally substituted cycloalkyl radical, preferably having 4 to 8 carbon atoms, especially a cyclohexyl radical, an optionally substituted aryl radical, preferably having 6 to 18 carbon atoms, a halogen, preferably fluorine, chlorine or bromine, or a radical of the formula (III) O
~
O ~ R 6 ~zzz>
in which R6 is a linear or branched alkyl radical having 1 to 6 carbon atoms, preferably a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl or n-hexyl radical, especially an ethyl radical.
Compounds (II) which are very particularly favourable in this context have hydrogen as R4. R3 is preferably an alkyl radical having 1 to 4 carbon atoms, especially a methyl radical. R5 is appropriately an alkyl radical having 1 to 4 carbon atoms, especially a tert-butyl radical.
For the purposes of the present invention, compounds of the formula (IIa) have also been found to be suitable.
OH
~ (IIa) The compound of the formula (IIb) has also been found to be particularly favourable:
OH
~ (IIb) where: R5 = tert-butyl.
The compound is sold under the brand Topanol A by Ciba.
In addition, favourable results can also be achieved using compounds of the formula (IV) OH
~
O
'R-C-(CH2)~ c-O Rg (IV) P
' R0W
OH
where o is an integer in the range of 1 to 4 and p is 1 or 2, preferably 2, where the R3 radicals are each as defined above, where R' is hydrogen or a linear or branched alkyl radical, preferably having 1 , CA 02642603 2008-08-15 to 8 carbon atoms, especially a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl or an n-octyl radical, especially a methyl radical, and where R8 is a monovalent alkyl group or divalent alkylene group, preferably a linear, a,c)-divalent alkylene group, preferably having 1 to 8 carbon atoms, especially a methyl, methylene, ethyl, 1,2-ethylene, n-propyl, 1,3-n-propylene, isopropyl, n-butyl, isobutyl, tert-butyl, 1,4-butylene, n-pentyl, 1,5-pentylene, n-hexyl, 1,6-hexylene, n-heptyl, 1,7-heptylene, n-octyl or a 1,8-octylene group, which more preferably has 1 to 4, most preferably 2, carbon atoms.
A particularly preferred compound of the formula (IV) is glycol bisL3,3-bis(41-hydroxy-3'-tert-butylphenyl)-butanoate] .
In a very particularly preferred embodiment of the present invention, a stabilizer mixture is used which comprises a) at least one compound of the formula (I) b) at least one compound of the formula (II) or (IV) and c) at least one compound of the formula (V) 9 Q* 9 (v) H OH
where the R9 radicals are each independently a linear or branched alkyl radical, preferably having 1 to 6, especially having 1 to 4, carbon atoms, such as a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or a tert-butyl radical, especially a methyl radical.
~ (IIa) The compound of the formula (IIb) has also been found to be particularly favourable:
OH
~ (IIb) where: R5 = tert-butyl.
The compound is sold under the brand Topanol A by Ciba.
In addition, favourable results can also be achieved using compounds of the formula (IV) OH
~
O
'R-C-(CH2)~ c-O Rg (IV) P
' R0W
OH
where o is an integer in the range of 1 to 4 and p is 1 or 2, preferably 2, where the R3 radicals are each as defined above, where R' is hydrogen or a linear or branched alkyl radical, preferably having 1 , CA 02642603 2008-08-15 to 8 carbon atoms, especially a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl or an n-octyl radical, especially a methyl radical, and where R8 is a monovalent alkyl group or divalent alkylene group, preferably a linear, a,c)-divalent alkylene group, preferably having 1 to 8 carbon atoms, especially a methyl, methylene, ethyl, 1,2-ethylene, n-propyl, 1,3-n-propylene, isopropyl, n-butyl, isobutyl, tert-butyl, 1,4-butylene, n-pentyl, 1,5-pentylene, n-hexyl, 1,6-hexylene, n-heptyl, 1,7-heptylene, n-octyl or a 1,8-octylene group, which more preferably has 1 to 4, most preferably 2, carbon atoms.
A particularly preferred compound of the formula (IV) is glycol bisL3,3-bis(41-hydroxy-3'-tert-butylphenyl)-butanoate] .
In a very particularly preferred embodiment of the present invention, a stabilizer mixture is used which comprises a) at least one compound of the formula (I) b) at least one compound of the formula (II) or (IV) and c) at least one compound of the formula (V) 9 Q* 9 (v) H OH
where the R9 radicals are each independently a linear or branched alkyl radical, preferably having 1 to 6, especially having 1 to 4, carbon atoms, such as a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or a tert-butyl radical, especially a methyl radical.
The compound of the formula (V) is sold under the brand Tempol by Ciba and under the name 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl by Degussa GmbH.
The weight ratio of the compound (I) to the compound (II) or (IV) and to the compound (V) is preferably in the range of 1:0.1 - 25.0:0.01 - 1Ø
Based on the (meth)acrylic anhydride, the proportion of the stabilizers individually or as a mixture is preferably 0.001 to 2.0o by weight.
Owing to the hydrolysis sensitivity of the reactants, it is appropriate to work under substantially anhydrous conditions. Moreover, the reactants used are dried substantially completely. In addition, the use of an inert gas atmosphere, especially of dry nitrogen and/or argon in the performance of the alkoxylation step has also been found to be very particularly useful. In the subsequent reaction with (meth)acrylic anhydride, in contrast, oxygen should be present, either in a mixture with the inert gases mentioned or as a dry air atmosphere, in order to increase the stabilization against polymerization.
Possible fields of use of the alkoxypolyoxyalkylene (meth)acrylates are already known. They are suitable, inter alia, for preparing dispersants.
The invention will be illustrated in more detail hereinafter by several inventive examples, without any intention that it be restricted to these specific embodiments.
The length of the polyalkylene block was determined by , CA 02642603 2008-08-15 withdrawing a small sample after step b) and determining the OH number.
Examples Example 1 Apparatus: 2 1 Buchi jacketed glass autoclave with manometer, mechanical stirrer, internal Pt 100 temperature sensor, inlet tube and oil circulation thermostat.
The reactor is evacuated, filled with nitrogen and charged with 6.6 g of a 30% solution of sodium methoxide in methanol (NM 30, Degussa AG). 6 g of dry methanol are added and the mixture is heated to 1000C, and 756 g of ethylene oxide are pumped in within 2 h, such that a pressure of 6 bar is not exceeded. Thereafter, reaction is allowed to continue at this temperature for a further 0.5 h. The mixture is cooled to 800C and unconsumed ethylene oxide is drawn off under reduced pressure (approx. 150 mbar) (time: approx. 0.5 h). A sample (10 g) is withdrawn for hydroxyl number determination, and 83.6 g of inethacrylic anhydride which contain 3.4 g of hydroquinone monomethyl ether (HQME) and 0.17 g of 2,6-dimethyl-4-tert-butylphenol (Topanol A) and 0.08 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (Tempol ) in dissolved form are added to the reactor, and the mixture is heated at standard pressure with slow introduction of air to 900C for 6 h.
After cooling to room temperature, the reaction product is withdrawn, weighed and admixed with the same amount of water. 1700 g of an aqueous methacrylic acid-containing methoxypolyethylene glycol 2000 methacrylate solution are obtained.
Analytical data:
OH number of the 10 g sample consisting of methoxypolyethylene glycol 2000: 27 mg KOH/g Determination of the molar mass:
M=(molar mass of potassium hydroxide) *100/ (OH number) _ 5600/27 = 2074 End product: Water content: 500 (Karl-Fischer titration) Acid number: 23 mg KOH/g (titration) Hydroxyl number (calculated on dry substance): 1 mg KOH/g HQME content: 25 ppm (determined by liquid chromatography) Topanol A: 80 ppm (determined by liquid chromatography) Tempol: content below the detection limit The content of HQME has declined compared to the initial weight (2000 ppm based on aqueous product solution) as a result of side reactions, as has the Tempol content (initial weight 47 ppm based on aqueous product solution). Compared to this, the content of Topanol A is reduced only from 100 ppm to 80 ppm.
The weight ratio of the compound (I) to the compound (II) or (IV) and to the compound (V) is preferably in the range of 1:0.1 - 25.0:0.01 - 1Ø
Based on the (meth)acrylic anhydride, the proportion of the stabilizers individually or as a mixture is preferably 0.001 to 2.0o by weight.
Owing to the hydrolysis sensitivity of the reactants, it is appropriate to work under substantially anhydrous conditions. Moreover, the reactants used are dried substantially completely. In addition, the use of an inert gas atmosphere, especially of dry nitrogen and/or argon in the performance of the alkoxylation step has also been found to be very particularly useful. In the subsequent reaction with (meth)acrylic anhydride, in contrast, oxygen should be present, either in a mixture with the inert gases mentioned or as a dry air atmosphere, in order to increase the stabilization against polymerization.
Possible fields of use of the alkoxypolyoxyalkylene (meth)acrylates are already known. They are suitable, inter alia, for preparing dispersants.
The invention will be illustrated in more detail hereinafter by several inventive examples, without any intention that it be restricted to these specific embodiments.
The length of the polyalkylene block was determined by , CA 02642603 2008-08-15 withdrawing a small sample after step b) and determining the OH number.
Examples Example 1 Apparatus: 2 1 Buchi jacketed glass autoclave with manometer, mechanical stirrer, internal Pt 100 temperature sensor, inlet tube and oil circulation thermostat.
The reactor is evacuated, filled with nitrogen and charged with 6.6 g of a 30% solution of sodium methoxide in methanol (NM 30, Degussa AG). 6 g of dry methanol are added and the mixture is heated to 1000C, and 756 g of ethylene oxide are pumped in within 2 h, such that a pressure of 6 bar is not exceeded. Thereafter, reaction is allowed to continue at this temperature for a further 0.5 h. The mixture is cooled to 800C and unconsumed ethylene oxide is drawn off under reduced pressure (approx. 150 mbar) (time: approx. 0.5 h). A sample (10 g) is withdrawn for hydroxyl number determination, and 83.6 g of inethacrylic anhydride which contain 3.4 g of hydroquinone monomethyl ether (HQME) and 0.17 g of 2,6-dimethyl-4-tert-butylphenol (Topanol A) and 0.08 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (Tempol ) in dissolved form are added to the reactor, and the mixture is heated at standard pressure with slow introduction of air to 900C for 6 h.
After cooling to room temperature, the reaction product is withdrawn, weighed and admixed with the same amount of water. 1700 g of an aqueous methacrylic acid-containing methoxypolyethylene glycol 2000 methacrylate solution are obtained.
Analytical data:
OH number of the 10 g sample consisting of methoxypolyethylene glycol 2000: 27 mg KOH/g Determination of the molar mass:
M=(molar mass of potassium hydroxide) *100/ (OH number) _ 5600/27 = 2074 End product: Water content: 500 (Karl-Fischer titration) Acid number: 23 mg KOH/g (titration) Hydroxyl number (calculated on dry substance): 1 mg KOH/g HQME content: 25 ppm (determined by liquid chromatography) Topanol A: 80 ppm (determined by liquid chromatography) Tempol: content below the detection limit The content of HQME has declined compared to the initial weight (2000 ppm based on aqueous product solution) as a result of side reactions, as has the Tempol content (initial weight 47 ppm based on aqueous product solution). Compared to this, the content of Topanol A is reduced only from 100 ppm to 80 ppm.
Example 2 As Example 1, except with use of 2.64 g of NM30 solution and 12.3 g of inethyltriglycol instead of the methanol.
Reaction is effected with 605 g of ethylene oxide in 1.5 h. After the sampling, 28 g of inethacrylic anhydride which contains 2.5 g of HQME, 0.06 g of Tempol and 0.06 g of Topanol A in dissolved form are added. After the reaction and water addition have ended, 1270 g of aqueous methoxypolyethylene glycol 5000 methacrylate solution are obtained.
Analytical data:
OH number of the 10 g sample, consisting of methoxypolyethylene glycol 5000: 11 mg KOH/g End product: Water content: 510 (Karl-Fischer titration) Acid number: 9.5 mg KOH/g (titration) Hydroxyl number (calculated on dry substance): 1.5 mg KOH/g Example 3 As Example 1, except with use of 13.2 g of NM30 solution and 12 g of inethanol. Reaction is effected with 737 g of ethylene oxide in 2 h. After the sampling, 174 g of methacrylic anhydride which contains 3.7 g of HQME, 0.09 g of Tempol and 0.35 g of Topanol A in dissolved form are added. After the reaction and water addition have ended, 1880 g of aqueous methoxypolyethylene glycol 1000 methacrylate solution are obtained.
Analytical data:
OH number of the 10 g sample, consisting of methoxypolyethylene glycol 1000: 55 mg KOH/g End product: Water content: 490 (Karl-Fischer titration) Acid number: 43 mg KOH/g (titration) Hydroxyl number (calculated on dry substance): 1 mg KOH/g Example 4 As Example 1, except with use of 18 g of NM30 solution and 16.5 g of inethanol. Reaction is effected with 760 g of ethylene oxide in 2 h. After the sampling, 242 g of methacrylic anhydride which contains 4.2 g of HQME, 0.1 g of Tempol and 0.5 g of Topanol A in dissolved form are added. After the reaction and water addition have ended, 2080 g of aqueous methacrylic acid-containing methoxypolyethylene glycol 750 methacrylate solution are obtained.
Analytical data:
OH number of the 10 g sample, consisting of methoxypolyethylene glycol 750: 75 mg KOH/g End product: Water content: 500 (Karl-Fischer titration) Acid number: 55 mg KOH/g (titration) Hydroxyl number (calculated on dry substance): 2 mg KOH/g Example 5 As Example 1, except wi.th use of 26.4 g of NM30 solution and 24 g of inethanol. Reaction is effected with 737 g of ethylene oxide in 2 h. After the sampling, 359 g of methacrylic anhydride which contains 4.6 g of HQME, 0.1 g of Tempol and 0.72 g of Topanol A in dissolved form are added. After the reaction and water addition have ended, 2300 g of aqueous methacrylic acid-containing methoxypolyethylene glycol 500 methacrylate solution are obtained.
Analytical data:
OH number of the 10 g sample, consisting of methoxypolyethylene glycol 500: 110 mg KOH/g End product: Water content: 52 s (Karl-Fischer titration) Acid number: 76 mg KOH/g (titration) Hydroxyl number (calculated on dry substance): 2.5 mg KOH/g Example 6 As Example 1, except with use of 39.6 g of NM30 solution and 36 g of inethanol. Reaction is effected with 774 g of ethylene oxide in 2.5 h. After the sampling, 554 g of methacrylic anhydride which contains 5.6 g of HQME, 0.14 g of Tempol and 1. 11 g of Topanol A in dissolved form are added. After the reaction and water addition have ended, 2800 g of aqueous methacrylic acid-containing methoxypolyethylene glycol 350 methacrylate solution are obtained.
Analytical data:
OH number of the 10 g sample, consisting of methoxypolyethylene glycol 350: 155 mg KOH/g End product: Water content: 500 (Karl-Fischer titration) Acid number: 99 mg KOH/g (titration) Hydroxyl number (calculated on dry substance): 2.1 mg KOH/g Example 7 As Example 1, except that, after the sampling, 70 g of acrylic anhydride which contains 3.3 g of HQME, 0.08 g of Tempol and 0.14 g of Topanol A in dissolved form are added. After the reaction and water addition have ended, 1600 g of aqueous acrylic acid-containing methoxypolyethylene glycol 2000 acrylate solution are obtained.
Analytical data:
OH number of the 10 g sample, consisting of methoxypolyethylene glycol 2000: 26 mg KOH/g End product: Water content: 4906 (Karl-Fischer titration) Acid number: 24 mg KOH/g (titration) Hydroxyl number (calculated on dry substance): 2 mg KOH/g Example 8 As Example 1, except that, instead of the sodium methoxide solution and the methanol, 4.1 g of potassium tert-butoxide and 27 g of dry n-butanol are used.
Reaction is effected with 971 g of propylene oxide in 4 h. After the sampling, 115 g of inethacrylic anhydride which contains 4.5 g of HQME, 0.11 g of Tempol and 0.23 g of Topanol A in dissolved form are added. After the reaction and water addition have ended, 2200 g of aqueous methacrylic acid-containing butoxypolypropylene . CA 02642603 2008-08-15 glycol 2000 methacrylate solution are obtained.
Analytical data:
OH number of the 10 g sample, consisting of butoxypolypropylene glycol 2000: 25 mg KOH/g End product: Water content: 50% (Karl-Fischer titration) Acid number: 24 mg KOH/g (titration) Hydroxyl number (calculated on dry substance): 1.2 mg KOH/g Example 9 As Example 8, except that reaction is effected successively with 486 g of ethylene oxide and 486 g of propylene oxide in a total of 4 h. After the sampling, 115 g of inethacrylic anhydride which contains 4.5 g of HQME, 0.11 g of Tempol and 0.23 g of Topanol A in dissolved form are added. After the reaction and water addition have ended, 2200 g of aqueous methacrylic acid-containing butoxypolyethylene polypropylene glycol 2000 methacrylate solution are obtained.
Analytical data:
OH number of the 10 g sample, consisting of butoxy-polyethylene polypropylene glycol 2000: 28 mg KOH/g End product: Water content: 50% (Karl-Fischer titration) Acid number: 23.5 mg KOH/g (titration) Hydroxyl number (calculated on dry substance): 1 mg KOH/g Example 10 As Example 1, except using 18 g of NM30 solution and 261 g of C16-18 alcohol (Hydrenol D, Cognis). At 100 C/150 mbar, the methanol fraction is drawn off, then the mixture is blanketed with nitrogen and reacted with 1100 g of ethylene oxide. After the sampling, 229 g of methacrylic anhydride which contains 6.3 g of HQME, 0.16 g of Tempol and 0.46 g of Topanol A in dissolved form are added. After the reaction and water addition have ended, 3190 g of aqueous methacrylic acid-containing alkoxypolyethylene glycol 1100 methacrylate solution are obtained.
Analytical data:
OH number of the 10 g sample, consisting of C16_18 -------- ----alkoxypolyethylene glycol methacrylate 1100: 50 mg KOH/g End product: Water content: 5106 (Karl-Fischer titration) Acid number: 40 mg KOH/g (titration) Hydroxyl number (calculated on dry substance): 1.8 mg KOH/g Example 11 (noninventive, comparative example):
Separate ethoxylation and methacrylation according to the prior art Apparatus: 2 1 Buchi jacketed glass autoclave with manometer, mechanical stirrer, internal Pt 100 tempera-ture sensor, inlet tube and oil circulation thermostat.
The reactor is evacuated, filled with nitrogen and charged with 6.6 g of a 30o solution of sodium methoxide in methanol (NM 30, Degussa AG). Another 6 g of dry methanol are added, the mixture is heated to 1000C and 756 g of ethylene oxide are pumped in within 2 h, such that a pressure of 6 bar is not exceeded. Thereafter, the reaction is allowed to continue at this temperature for a further 0.5 h. The mixture is cooled to 800C and unconsumed ethylene oxide is drawn off under reduced pressure (approx. 150 mbar) (duration: approx. 0.5 h).
The methoxypolyethylene glycol 2000 formed is withdrawn via the bottom valve and a sample (10 g) is taken for hydroxyl number determination.
Yield: 753 g(980 of theory) OH number of the 10 g sample, consisting of inethoxy-polyethylene glycol 2000: 28 mg KOH/g The product is introduced into a 2 1 round-bottomed flask with stirrer and reflux condenser with 83.6 g of methacrylic anhydride which comprises 3.4 g of hydroquinone monomethyl ether (HQME) and 0.17 g of 2,6-dimethyl-4-tert-butylphenol (Topanol A) and 0.08 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (Tempol ) in dissolved form, and heated to 900C at standard pressure while passing air through slowly. After 6 h, a sample is taken and, according to NMR
spectroscopy, has a conversion of 900. After a total of 8 h at 900C, the mixture is cooled to room temperature, and the reaction product is withdrawn, weighed and admixed with the same amount of water. 1650 g of an aqueous methacrylic acid-containing methoxypolyethylene glycol 2000 methacrylate solution are obtained.
End product: Water content: 49% (Karl-Fischer titration) Acid number: 24 mg KOH/g (titration) Hydroxyl number (calculated on dry substance): 1 mg KOH/g Example 12 As Example 1, except using 1.44 g of sodium hydroxide and 60 g of triethylene glycol monomethyl ether. After heating to 1000C, water of reaction formed is drawn off under reduced pressure for 0.5 h. 624 g of ethylene oxide are then pumped in within 1.5 h. After the sampling, 83.6 g of inethacrylic anhydride which contains 3.4 g of hydroquinone monomethyl ether (HQME) and 0.17 g of 2,6-dimethyl-4-tert-butylphenol (Topanol A) and 0.08 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (Tempol ) in dissolved form are introduced into the reactor at standard pressure while slowly passing air through at 900C for 6 h.
After cooling to room temperature, the reaction product is withdrawn, weighed and admixed with the same amount of water. 1500 g of an aqueous methacrylic acid-containing methoxypolyethylene glycol 2000 methacrylate solution are obtained.
OH number of the 10 g sample consisting of inethoxy-polyethylene glycol 2000: 29 mg KOH/g End product: Water content: 510 (Karl-Fischer titration) Acid number: 26 mg KOH/g (titration) Hydroxyl number (calculated on dry substance): 1.5 mg KOH/g Example 13 As Example 1, except that the stabilizer added to the methacrylic anhydride is only 3.4 g of Topanol A . The resulting 1680 g of a methoxypolyethylene glycol 2000 methacrylate solution in water contain 1520 ppm of Topanol A , i.e. of the 2000 ppm of stabilizer used, only a small portion has been consumed by side reactions.
Example 14 (comparative example) As Example 1, except that the stabilizer added to the methacrylic anhydride is only 0.85 g of phenothiazine (500 ppm based on aqueous product solution). The resulting 1690 g of a methoxypolyethylene glycol 2000 methacrylate solution in water contain 490 ppm of phenothiazine (determined by liquid chromatography).
After 1 week of storage in diffuse daylight, the product solution has polymer fractions (determined by NMR spectroscopy).
Example 15 (comparative example) As Example 1, except that the stabilizer added to the methacrylic anhydride is 0.85 g of 2,6-di(tert-butyl)-4-methylphenol (Topanol O ) (500 ppm based on aqueous product solution). The resulting 1700 g of a methoxypolyethylene glycol 2000 methacrylate solution in water contain 480 ppm of Topanol O (determined by liquid chromatography). The product solution is stable but is cloudy.
Example 16 (comparative example) As Example 1, except that the stabilizer added to the methacrylic anhydride is 0.85 g of Tempol (500 ppm based on aqueous product solution). The resulting methoxypolyethylene glycol 2000 methacrylate solution in water contains 50 mola of polymer (determined by NMR spectroscopy).
Reaction is effected with 605 g of ethylene oxide in 1.5 h. After the sampling, 28 g of inethacrylic anhydride which contains 2.5 g of HQME, 0.06 g of Tempol and 0.06 g of Topanol A in dissolved form are added. After the reaction and water addition have ended, 1270 g of aqueous methoxypolyethylene glycol 5000 methacrylate solution are obtained.
Analytical data:
OH number of the 10 g sample, consisting of methoxypolyethylene glycol 5000: 11 mg KOH/g End product: Water content: 510 (Karl-Fischer titration) Acid number: 9.5 mg KOH/g (titration) Hydroxyl number (calculated on dry substance): 1.5 mg KOH/g Example 3 As Example 1, except with use of 13.2 g of NM30 solution and 12 g of inethanol. Reaction is effected with 737 g of ethylene oxide in 2 h. After the sampling, 174 g of methacrylic anhydride which contains 3.7 g of HQME, 0.09 g of Tempol and 0.35 g of Topanol A in dissolved form are added. After the reaction and water addition have ended, 1880 g of aqueous methoxypolyethylene glycol 1000 methacrylate solution are obtained.
Analytical data:
OH number of the 10 g sample, consisting of methoxypolyethylene glycol 1000: 55 mg KOH/g End product: Water content: 490 (Karl-Fischer titration) Acid number: 43 mg KOH/g (titration) Hydroxyl number (calculated on dry substance): 1 mg KOH/g Example 4 As Example 1, except with use of 18 g of NM30 solution and 16.5 g of inethanol. Reaction is effected with 760 g of ethylene oxide in 2 h. After the sampling, 242 g of methacrylic anhydride which contains 4.2 g of HQME, 0.1 g of Tempol and 0.5 g of Topanol A in dissolved form are added. After the reaction and water addition have ended, 2080 g of aqueous methacrylic acid-containing methoxypolyethylene glycol 750 methacrylate solution are obtained.
Analytical data:
OH number of the 10 g sample, consisting of methoxypolyethylene glycol 750: 75 mg KOH/g End product: Water content: 500 (Karl-Fischer titration) Acid number: 55 mg KOH/g (titration) Hydroxyl number (calculated on dry substance): 2 mg KOH/g Example 5 As Example 1, except wi.th use of 26.4 g of NM30 solution and 24 g of inethanol. Reaction is effected with 737 g of ethylene oxide in 2 h. After the sampling, 359 g of methacrylic anhydride which contains 4.6 g of HQME, 0.1 g of Tempol and 0.72 g of Topanol A in dissolved form are added. After the reaction and water addition have ended, 2300 g of aqueous methacrylic acid-containing methoxypolyethylene glycol 500 methacrylate solution are obtained.
Analytical data:
OH number of the 10 g sample, consisting of methoxypolyethylene glycol 500: 110 mg KOH/g End product: Water content: 52 s (Karl-Fischer titration) Acid number: 76 mg KOH/g (titration) Hydroxyl number (calculated on dry substance): 2.5 mg KOH/g Example 6 As Example 1, except with use of 39.6 g of NM30 solution and 36 g of inethanol. Reaction is effected with 774 g of ethylene oxide in 2.5 h. After the sampling, 554 g of methacrylic anhydride which contains 5.6 g of HQME, 0.14 g of Tempol and 1. 11 g of Topanol A in dissolved form are added. After the reaction and water addition have ended, 2800 g of aqueous methacrylic acid-containing methoxypolyethylene glycol 350 methacrylate solution are obtained.
Analytical data:
OH number of the 10 g sample, consisting of methoxypolyethylene glycol 350: 155 mg KOH/g End product: Water content: 500 (Karl-Fischer titration) Acid number: 99 mg KOH/g (titration) Hydroxyl number (calculated on dry substance): 2.1 mg KOH/g Example 7 As Example 1, except that, after the sampling, 70 g of acrylic anhydride which contains 3.3 g of HQME, 0.08 g of Tempol and 0.14 g of Topanol A in dissolved form are added. After the reaction and water addition have ended, 1600 g of aqueous acrylic acid-containing methoxypolyethylene glycol 2000 acrylate solution are obtained.
Analytical data:
OH number of the 10 g sample, consisting of methoxypolyethylene glycol 2000: 26 mg KOH/g End product: Water content: 4906 (Karl-Fischer titration) Acid number: 24 mg KOH/g (titration) Hydroxyl number (calculated on dry substance): 2 mg KOH/g Example 8 As Example 1, except that, instead of the sodium methoxide solution and the methanol, 4.1 g of potassium tert-butoxide and 27 g of dry n-butanol are used.
Reaction is effected with 971 g of propylene oxide in 4 h. After the sampling, 115 g of inethacrylic anhydride which contains 4.5 g of HQME, 0.11 g of Tempol and 0.23 g of Topanol A in dissolved form are added. After the reaction and water addition have ended, 2200 g of aqueous methacrylic acid-containing butoxypolypropylene . CA 02642603 2008-08-15 glycol 2000 methacrylate solution are obtained.
Analytical data:
OH number of the 10 g sample, consisting of butoxypolypropylene glycol 2000: 25 mg KOH/g End product: Water content: 50% (Karl-Fischer titration) Acid number: 24 mg KOH/g (titration) Hydroxyl number (calculated on dry substance): 1.2 mg KOH/g Example 9 As Example 8, except that reaction is effected successively with 486 g of ethylene oxide and 486 g of propylene oxide in a total of 4 h. After the sampling, 115 g of inethacrylic anhydride which contains 4.5 g of HQME, 0.11 g of Tempol and 0.23 g of Topanol A in dissolved form are added. After the reaction and water addition have ended, 2200 g of aqueous methacrylic acid-containing butoxypolyethylene polypropylene glycol 2000 methacrylate solution are obtained.
Analytical data:
OH number of the 10 g sample, consisting of butoxy-polyethylene polypropylene glycol 2000: 28 mg KOH/g End product: Water content: 50% (Karl-Fischer titration) Acid number: 23.5 mg KOH/g (titration) Hydroxyl number (calculated on dry substance): 1 mg KOH/g Example 10 As Example 1, except using 18 g of NM30 solution and 261 g of C16-18 alcohol (Hydrenol D, Cognis). At 100 C/150 mbar, the methanol fraction is drawn off, then the mixture is blanketed with nitrogen and reacted with 1100 g of ethylene oxide. After the sampling, 229 g of methacrylic anhydride which contains 6.3 g of HQME, 0.16 g of Tempol and 0.46 g of Topanol A in dissolved form are added. After the reaction and water addition have ended, 3190 g of aqueous methacrylic acid-containing alkoxypolyethylene glycol 1100 methacrylate solution are obtained.
Analytical data:
OH number of the 10 g sample, consisting of C16_18 -------- ----alkoxypolyethylene glycol methacrylate 1100: 50 mg KOH/g End product: Water content: 5106 (Karl-Fischer titration) Acid number: 40 mg KOH/g (titration) Hydroxyl number (calculated on dry substance): 1.8 mg KOH/g Example 11 (noninventive, comparative example):
Separate ethoxylation and methacrylation according to the prior art Apparatus: 2 1 Buchi jacketed glass autoclave with manometer, mechanical stirrer, internal Pt 100 tempera-ture sensor, inlet tube and oil circulation thermostat.
The reactor is evacuated, filled with nitrogen and charged with 6.6 g of a 30o solution of sodium methoxide in methanol (NM 30, Degussa AG). Another 6 g of dry methanol are added, the mixture is heated to 1000C and 756 g of ethylene oxide are pumped in within 2 h, such that a pressure of 6 bar is not exceeded. Thereafter, the reaction is allowed to continue at this temperature for a further 0.5 h. The mixture is cooled to 800C and unconsumed ethylene oxide is drawn off under reduced pressure (approx. 150 mbar) (duration: approx. 0.5 h).
The methoxypolyethylene glycol 2000 formed is withdrawn via the bottom valve and a sample (10 g) is taken for hydroxyl number determination.
Yield: 753 g(980 of theory) OH number of the 10 g sample, consisting of inethoxy-polyethylene glycol 2000: 28 mg KOH/g The product is introduced into a 2 1 round-bottomed flask with stirrer and reflux condenser with 83.6 g of methacrylic anhydride which comprises 3.4 g of hydroquinone monomethyl ether (HQME) and 0.17 g of 2,6-dimethyl-4-tert-butylphenol (Topanol A) and 0.08 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (Tempol ) in dissolved form, and heated to 900C at standard pressure while passing air through slowly. After 6 h, a sample is taken and, according to NMR
spectroscopy, has a conversion of 900. After a total of 8 h at 900C, the mixture is cooled to room temperature, and the reaction product is withdrawn, weighed and admixed with the same amount of water. 1650 g of an aqueous methacrylic acid-containing methoxypolyethylene glycol 2000 methacrylate solution are obtained.
End product: Water content: 49% (Karl-Fischer titration) Acid number: 24 mg KOH/g (titration) Hydroxyl number (calculated on dry substance): 1 mg KOH/g Example 12 As Example 1, except using 1.44 g of sodium hydroxide and 60 g of triethylene glycol monomethyl ether. After heating to 1000C, water of reaction formed is drawn off under reduced pressure for 0.5 h. 624 g of ethylene oxide are then pumped in within 1.5 h. After the sampling, 83.6 g of inethacrylic anhydride which contains 3.4 g of hydroquinone monomethyl ether (HQME) and 0.17 g of 2,6-dimethyl-4-tert-butylphenol (Topanol A) and 0.08 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (Tempol ) in dissolved form are introduced into the reactor at standard pressure while slowly passing air through at 900C for 6 h.
After cooling to room temperature, the reaction product is withdrawn, weighed and admixed with the same amount of water. 1500 g of an aqueous methacrylic acid-containing methoxypolyethylene glycol 2000 methacrylate solution are obtained.
OH number of the 10 g sample consisting of inethoxy-polyethylene glycol 2000: 29 mg KOH/g End product: Water content: 510 (Karl-Fischer titration) Acid number: 26 mg KOH/g (titration) Hydroxyl number (calculated on dry substance): 1.5 mg KOH/g Example 13 As Example 1, except that the stabilizer added to the methacrylic anhydride is only 3.4 g of Topanol A . The resulting 1680 g of a methoxypolyethylene glycol 2000 methacrylate solution in water contain 1520 ppm of Topanol A , i.e. of the 2000 ppm of stabilizer used, only a small portion has been consumed by side reactions.
Example 14 (comparative example) As Example 1, except that the stabilizer added to the methacrylic anhydride is only 0.85 g of phenothiazine (500 ppm based on aqueous product solution). The resulting 1690 g of a methoxypolyethylene glycol 2000 methacrylate solution in water contain 490 ppm of phenothiazine (determined by liquid chromatography).
After 1 week of storage in diffuse daylight, the product solution has polymer fractions (determined by NMR spectroscopy).
Example 15 (comparative example) As Example 1, except that the stabilizer added to the methacrylic anhydride is 0.85 g of 2,6-di(tert-butyl)-4-methylphenol (Topanol O ) (500 ppm based on aqueous product solution). The resulting 1700 g of a methoxypolyethylene glycol 2000 methacrylate solution in water contain 480 ppm of Topanol O (determined by liquid chromatography). The product solution is stable but is cloudy.
Example 16 (comparative example) As Example 1, except that the stabilizer added to the methacrylic anhydride is 0.85 g of Tempol (500 ppm based on aqueous product solution). The resulting methoxypolyethylene glycol 2000 methacrylate solution in water contains 50 mola of polymer (determined by NMR spectroscopy).
Claims (16)
1. Process for preparing an alkoxypolyoxyalkylene (meth)acrylate in which a) at least one metal alkoxide MetOR10 is initially charged, where Met is lithium, sodium, potassium, rubidium or caesium and where R10 is a linear or branched alkyl radical, b) at least one alcohol R12OH is added, where R12 is a linear or branched, optionally alkoxylated alkyl radical, preferably having 1 to 18 carbon atoms, in particular a methyl, 2-methoxyethyl,
2-(2-methoxyethoxy)ethyl, 2-(2-(2-methoxyethoxy)ethoxy)ethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or an octadecyl radical, where the molar mass of R12 is less than the molar mass of the inventive alkoxypolyoxyalkylenes, c) at least one alkylene oxide of the formula (VI) is added and reacted with the metal alkoxide where the R11 radicals are each independently hydrogen or a linear or branched alkyl radical, preferably having 1 to 8 carbon atoms, in particular a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl or an n-octyl radical, and d) (meth) acrylic anhydride is added directly and reacted with the reaction product from step c).
2. Process according to Claim 1, characterized in that metal alkoxide where R10 = methyl, ethyl or tert-butyl is used.
2. Process according to Claim 1, characterized in that metal alkoxide where R10 = methyl, ethyl or tert-butyl is used.
3. Process according to Claim 1 or 2, characterized in that the reaction in step b) is performed in an alcohol R12OH which preferably satisfies the formula R12OH where the metal alkoxide and the alcohol appropriately have the same alkyl radical.
4. Process according to at least one of Claims 1 to 3, characterized in that the alkylene oxide used is ethylene oxide and/or propylene oxide.
5. Process according to at least one of Claims 1 to 4, characterized in that the reaction in step d) is performed in the presence of a stabilizer or a stabilizer mixture according to at least one of the preceding Claims 1 to 4.
6. Process according to Claim 5, characterized in that the (meth) acrylic anhydride:stabilizer or stabilizer mixture weight ratio is selected in the range of 100:0.5-15Ø
7. Process according to at least one of Claims 1 to 6, characterized in that the reaction in step b) is performed at a temperature in the range of 60°C to 150°C.
8. Process according to at least one of Claims 1 to 7, characterized in that the reaction in step c) is performed at a temperature in the range of 60°C to 150°C.
9. Process for preparing an alkoxypolyoxyalkylene (meth) acrylate in which a) at least one catalyst is used, b) at least one alcohol R12OH is added, c) at least one alkylene oxide of the formula (VI) is added and reacted with the metal alkoxide where the R11 radicals are each independently hydrogen or a linear or branched alkyl radical, and d) (meth) acrylic anhydride is added directly and reacted with the reaction product from step b).
10. Process according to Claim 9, characterized in that the stabilizer is used in amounts of 50 ppm to 5000 ppm, based on the sum of the masses of the reactants used.
11. Stabilizer mixture comprising I. at least one compound of the formula (I) where the R1 radicals are each independently hydrogen, a linear or branched alkyl radical, an optionally substituted cycloalkyl radical, an optionally substituted aryl radical or a halogen, and where R2 is a linear or branched alkyl radical, is an optionally substituted cycloalkyl radical or is an optionally substituted aryl radical, II. at least one compound of the formula (II) or of the formula (IV) where the R3, R4 and R5 radicals are each independently hydrogen, a linear or branched alkyl radical, an optionally substituted cycloalkyl radical, an optionally substituted aryl radical, a halogen or a radical of the formula (III) in which R6 is a linear or branched alkyl radical having 1 to 6 carbon atoms, where R7 is hydrogen or a linear or branched alkyl radical, and where R8 is a monovalent alkyl group or divalent alkylene group, III. at least one compound of the formula (V) where the R9 radicals are each independently a linear or branched alkyl radical or an optionally substituted cycloalkyl radical.
12. Stabilizer mixture according to Claim 11, characterized in that R1 is in each case hydrogen and R2 is an alkyl radical having 1 to 4 carbon atoms.
13. Stabilizer mixture according to Claim 11 or 12, characterized in that R3 is in each case an alkyl radical having 1 to 4 carbon atoms, R4 is in each case hydrogen and R5 is an alkyl radical having 1 to 4 carbon atoms.
14. Stabilizer mixture according to at least one of Claims 11-13, characterized in that R9 is in each case a methyl radical.
15. Stabilizer mixture according to at least one of Claims 11-14, characterized in that the weight ratio of the compound (I):compound (II) and/or compound (IV) :compound (V) is in the range of 1:0.1 - 25.0:0.01 - 1Ø
16. Process for preparing the compounds according to Claim 1, characterized in that, instead of the metal alkoxide MetOR10, a metal hydroxide MetOH is used, and its mixture with the alcohol R12OH is dewatered by methods known per se before the alkylene oxide is added.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006008998.7 | 2006-02-23 | ||
| DE102006008998A DE102006008998A1 (en) | 2006-02-23 | 2006-02-23 | Stabiliser mixture, especially for the production of alkoxypolyoxyalkylene (meth)acrylate, comprises a hydroquinone mono-ether, a phenolic antioxidant and a 2,2,6,6-tetra-substituted hydroxypiperidine derivative |
| PCT/EP2007/050875 WO2007096228A1 (en) | 2006-02-23 | 2007-01-30 | Process for preparing alkoxypolyoxyalkylene (meth)acrylates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2642603A1 true CA2642603A1 (en) | 2007-08-30 |
Family
ID=37908235
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002642603A Abandoned CA2642603A1 (en) | 2006-02-23 | 2007-01-30 | Process for preparing alkoxypolyoxyalkylene (meth)acrylates |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US7828271B2 (en) |
| EP (1) | EP1986987A1 (en) |
| JP (1) | JP2009527606A (en) |
| KR (1) | KR20080103536A (en) |
| CN (1) | CN101374797A (en) |
| AU (1) | AU2007217669A1 (en) |
| BR (1) | BRPI0708122A2 (en) |
| CA (1) | CA2642603A1 (en) |
| DE (1) | DE102006008998A1 (en) |
| MX (1) | MX2008010792A (en) |
| RU (1) | RU2440970C2 (en) |
| TW (1) | TW200804438A (en) |
| WO (1) | WO2007096228A1 (en) |
| ZA (1) | ZA200807273B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10314776A1 (en) * | 2003-03-31 | 2004-10-14 | Rohmax Additives Gmbh | Lubricating oil composition with good rubbing properties |
| DE102006006200B4 (en) * | 2006-02-09 | 2008-01-10 | Röhm Gmbh | Aqueous N-methylol-methacrylamide-methacrylamide mixture |
| KR101077303B1 (en) * | 2009-05-06 | 2011-10-26 | 삼성전기주식회사 | Composition for forming substrate, and prepreg and substrate using the same |
| CN102504127B (en) * | 2011-12-03 | 2014-05-07 | 南京瑞迪高新技术有限公司 | Polycarboxylic acid hyper-dispersant for dispersing lithium iron phosphate precursor |
| CN103160159B (en) * | 2011-12-09 | 2014-07-30 | 东莞市绿微康生物科技有限公司 | Surfactant for wastepaper deinking, and preparation method thereof |
| CN103145973B (en) * | 2013-01-28 | 2015-11-25 | 厦门巨晟机械工程有限公司 | A kind of method of producing poly glycol monomethyl ether |
| DE102014202963A1 (en) * | 2014-02-18 | 2015-08-20 | Basf Se | Process for the preparation of (meth) acrylic esters of polyalkoxy-containing alcohols |
| WO2018133972A1 (en) | 2017-01-20 | 2018-07-26 | Evonik Röhm Gmbh | Glycerol (meth)acrylate carboxylic ester having a long shelf life |
| EP3611155A1 (en) | 2018-08-16 | 2020-02-19 | Evonik Operations GmbH | Preparation of (meth)acrylic acid esters |
| KR102285438B1 (en) * | 2018-11-27 | 2021-08-02 | 주식회사 엘지화학 | Preparation method of acrylic acid ester compound |
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| US5322960A (en) | 1993-04-15 | 1994-06-21 | Nippon Shokubai Co., Ltd. | Method for inhibiting polymerization of (meth) acrylic acid and esters thereof |
| US5728872A (en) | 1994-06-27 | 1998-03-17 | Lutz Riemenschneider | Stabilized acrylic acid compositions |
| FR2739850B1 (en) | 1995-10-17 | 1997-12-05 | Atochem Elf Sa | PROCESS FOR THE MANUFACTURE OF ACRYLIC AND METHACRYLIC ESTERS OF HYDROPHOBIC CHAIN POLYALKOXYL ALCOHOLS |
| JPH10218988A (en) * | 1997-02-07 | 1998-08-18 | Kao Corp | Reactive fluoropolyether and its production |
| JP4385440B2 (en) * | 1999-06-08 | 2009-12-16 | 日油株式会社 | Polymerizable polyoxyalkylene monoalkyl ether derivative, polymer of the derivative, and dispersant containing the polymer |
| US6780928B1 (en) * | 1998-06-17 | 2004-08-24 | Nof Corporation | Polyoxyalkylene monoalkyl ether, process for producing the same, polymerizable polyoxyalkylene monoalkyl ether derivative, polymer of said derivative and dispersant comprising said polymer |
| DE19834360A1 (en) * | 1998-07-30 | 2000-02-03 | Bayer Ag | Process for the preparation of esters of (meth) acrylic acid |
| DE19938841A1 (en) * | 1999-08-17 | 2001-02-22 | Basf Ag | Inhibitor composition for the stabilization of radical polymerisable substances |
| DE19946136A1 (en) | 1999-09-27 | 2001-03-29 | Basf Ag | Inhibitor composition |
| FR2807045B1 (en) | 2000-03-31 | 2004-02-27 | Atofina | WATER-SOLUBLE ACRYLIC COPOLYMERS AND THEIR USE AS FLUIDIFIERS OR DISPERSANTS |
| BR0311498A (en) * | 2002-06-11 | 2005-03-15 | Basf Ag | ester f, processes for preparing the same and a cross-linked hydrogel, polymer, cross-linked hydrogel, use of a polymer, composition of matter, and uses of a reaction mixture, and an ester |
| JP2004339170A (en) * | 2003-05-16 | 2004-12-02 | Nippon Shokubai Co Ltd | (meth)acrylic acid alkali metal salt and method for producing the same |
| MXPA05012802A (en) | 2003-06-06 | 2006-02-22 | Basf Ag | (meth)acrylic ester for alkylenylene glycol and the use thereof. |
| JP2005015345A (en) * | 2003-06-23 | 2005-01-20 | Kuraray Co Ltd | Di(meth)acrylate mixture and polyether mixture |
| JP4718805B2 (en) * | 2004-08-02 | 2011-07-06 | 大阪有機化学工業株式会社 | Photocurable oligomer chain end (meth) acrylate production method |
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2006
- 2006-02-23 DE DE102006008998A patent/DE102006008998A1/en not_active Withdrawn
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2007
- 2007-01-30 BR BRPI0708122-7A patent/BRPI0708122A2/en not_active IP Right Cessation
- 2007-01-30 AU AU2007217669A patent/AU2007217669A1/en not_active Abandoned
- 2007-01-30 WO PCT/EP2007/050875 patent/WO2007096228A1/en active Application Filing
- 2007-01-30 JP JP2008555729A patent/JP2009527606A/en active Pending
- 2007-01-30 US US12/159,871 patent/US7828271B2/en not_active Expired - Fee Related
- 2007-01-30 RU RU2008134312/04A patent/RU2440970C2/en not_active IP Right Cessation
- 2007-01-30 CN CNA2007800038774A patent/CN101374797A/en active Pending
- 2007-01-30 KR KR1020087020682A patent/KR20080103536A/en not_active Application Discontinuation
- 2007-01-30 MX MX2008010792A patent/MX2008010792A/en not_active Application Discontinuation
- 2007-01-30 CA CA002642603A patent/CA2642603A1/en not_active Abandoned
- 2007-01-30 EP EP07704228A patent/EP1986987A1/en not_active Withdrawn
- 2007-02-15 TW TW096105822A patent/TW200804438A/en unknown
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Also Published As
| Publication number | Publication date |
|---|---|
| BRPI0708122A2 (en) | 2011-05-17 |
| EP1986987A1 (en) | 2008-11-05 |
| ZA200807273B (en) | 2009-08-26 |
| WO2007096228A1 (en) | 2007-08-30 |
| CN101374797A (en) | 2009-02-25 |
| JP2009527606A (en) | 2009-07-30 |
| DE102006008998A1 (en) | 2007-08-30 |
| TW200804438A (en) | 2008-01-16 |
| AU2007217669A1 (en) | 2007-08-30 |
| RU2008134312A (en) | 2010-03-27 |
| KR20080103536A (en) | 2008-11-27 |
| US7828271B2 (en) | 2010-11-09 |
| US20090001322A1 (en) | 2009-01-01 |
| MX2008010792A (en) | 2008-11-14 |
| RU2440970C2 (en) | 2012-01-27 |
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